Alkylaromatic Sulfonate Compositions From Mixed Hydrocarbons

ABSTRACT

Provided herein are various methods for forming alkylaromatic sulfonate compositions and blended alkylaromatic sulfonate compositions, and such compositions themselves. The methods of various embodiments include obtaining a C 8 -C 30  hydrocarbon mixture, optionally treating the mixture to concentrate the mixture in sulfonatable aromatics, and sulfonating the mixture to form the alkylaromatic sulfonates. The mixture or treated mixture may be blended with linear alkyl benzene (LAB) compositions and sulfonated, and/or the alkylaryl sulfonates may be blended with linear alkylbenzene sulfonate (LAS) compositions, to form the blended alkylaromatic sulfonates of some embodiments. These compositions and processes for making them may be tailored to serve a variety of end uses, such as detergents in cleaning solutions or for enhanced oil recovery operations, and/or as low foaming and/or hydrotropic additives in detergent formulations, and the like.

PRIORITY CLAIM

This application claims priority to and the benefit of U.S. Ser. No.62/382,343, filed Sep. 1, 2016 and is incorporated by reference in itsentirety.

FIELD OF THE INVENTION

The present invention relates to processes, systems, and apparatus formaking alkylaromatic sulfonate compositions, and such alkylaromaticsulfonate compositions themselves. The alkyl sulfonate compositions mayfind use as surfactants, in particular in detergent and/or soapapplications such as cleaning products, enhanced oil recoveryoperations, and the like.

BACKGROUND OF THE INVENTION

Alkylaromatic sulfonates are well known surfactants, finding use invarious detergent and similar applications. These compositions aretypically formed through the alkylation of benzene with partiallydehydrogenated paraffins in order to form a linear alkylbenzene (LAB),which comprises a hydrocarbyl radical appended to a benzene ring. TheLAB is then subjected to sulfonation, in which a sulfonate group ischemically bonded to a carbon atom in the benzene ring structure of theLAB. The resulting linear alkylbenzene sulfonate (LAS) thereforecontains a hydrophilic sulfonate group and a hydrophobic hydrocarbylportion. Alkylation and sulfonation processes useful for forming LAB andLAS compositions are well known. See, e.g., U.S. Pat. No. 6,887,839.

Petroleum sulfonates are another type of alkylaromatic sulfonate. Thesecompositions are formed from a simpler process of sulfonating crude oilor a crude oil distillation cut. Although the formation is simpler,these compositions typically suffer from significant drawbacks,including a very broad distribution of sulfonated aromatic species andthe presence of large amounts of inactive material such as saturates.

SUMMARY OF THE INVENTION

The present inventors have found that through a combination of treatmentsteps and/or blending, useful alkylaromatic sulfonate compositions canbe obtained from hydrocarbon mixtures such as crude oil distillationcuts, without the need for costly dehydrogenation/alkylation processesto form LABs from benzene and paraffins. Furthermore, surprisingly, ithas been discovered as part of the present work that certain compoundspreviously thought to be undesirable in an alkylaromatic sulfonatecomposition in fact provide advantageous properties in varioussurfactant applications.

Accordingly, in some aspects, the present invention relates to processesfor forming alkylaromatic sulfonate compositions, preferably withoutalkylation, as well as the alkylaromatic sulfonate compositionsthemselves. Processes of particular aspects include: (1) obtaining ahydrocarbon mixture; (2) treating the hydrocarbon mixture to obtain aprecursor alkylaromatic composition; and (3) sulfonating the precursoralkylaromatic composition, followed by neutralization if necessary, soas to obtain an alkylaromatic sulfonate composition. Processes accordingto some aspects further include one or more blending steps so as to forma blended alkylaromatic sulfonate composition. For instance, theprecursor alkylaromatic composition may be blended with a LABcomposition to form a blended precursor alkylaromatic composition whichis then sulfonated and, if needed, neutralized, and/or the alkylaromaticsulfonate composition is blended with a LAS composition, to form theblended alkylaromatic sulfonate composition. In processes according toyet other aspects, the (2) treating is optional, such that an untreatedhydrocarbon mixture may be sulfonated and then optionally blended with aLAS composition; or the untreated hydrocarbon mixture may be blendedwith a LAB composition followed by sulfonation of the blendedcomposition (again with optional further blending with a LAScomposition).

The hydrocarbon mixture may comprise, or consist essentially of, C₇-C₃₀hydrocarbon compounds, preferably C₁₆-C₂₈ (such as C₁₆-C₂₁)hydrocarbons; or in some aspects C₇-C₁₇ hydrocarbon compounds (e.g., foralkylaromatic sulfonate compositions useful in hydrotrope applications);or in further aspects C₇-C₆₀ hydrocarbon compounds (such broader rangeuseful, e.g., for alkylaromatic sulfonates intended for enhanced oilrecovery (EOR) applications). The hydrocarbon compounds comprise bothsaturated hydrocarbons (e.g., one or more of paraffin, single-ring, andmulti-ring saturated hydrocarbons) and unsaturated hydrocarbons(olefins, single ring aromatics, and multi-ring aromatics). Thehydrocarbon mixture may advantageously be a crude oil distillation cut,such as a cut having boiling range of 140° C.-420° C., or a cut havingnarrower boiling range within 140° C.-420° C. (e.g., 260° C.-420° C. or260° C.-340° C., which ranges may be useful for hydrotropeapplications). In yet other embodiments, particularly those in whichalkylaromatic sulfonate compositions are desired for EOR applications,broader boiling cuts (e.g., 100° C.-700° C., 120° C.-600° C., or 140°C.-500° C., with ranges from any of the foregoing lows to any of theforegoing highs also contemplated) may be preferred.

In some aspects, the hydrocarbon mixture is further treated to obtain aprecursor alkylaromatic composition having a composition tailored forsulfonation. Treating the hydrocarbon mixture may include subjecting thehydrocarbon mixture to any one or more of the following treatmentmethods: hydrotreating, hydrodesulfurization, catalytic cracking,catalytic reforming, solvent extraction, and solvent dewaxing.

Sulfonation may be carried out using any suitable process now or laterknown in the art for the attachment of a sulfonate group to an aromaticring in aromatic hydrocarbons. Such processes include sulfonating thearomatic ring of the aromatic hydrocarbons to form a sulfonic acid,which is then neutralized with base, and purified to yield thealkylaromatic sulfonate.

The alkylaromatic sulfonate compositions of certain aspects may obtain40-98% surfactant activity. Such compositions according to someembodiments are obtained from a process in accordance with the foregoingdescription. These compositions may serve as surfactants, and inparticular as detergents and/or as components of detergent formulations,e.g., for cleaning compositions and/or for use in enhanced oil recoveryoperations.

Blended alkylaromatic sulfonate compositions may be formed, such blendedsulfonate compositions comprising from 1-99 wt % alkylaromaticcompositions according to various embodiments herein, and 1-99 wt % of aLAS composition. The blended alkylaromatic sulfonate compositions ofsome embodiments are obtained from processes that include blending withLAB and/or LAS compositions in accordance with the foregoingdescriptions.

The present inventors have also discovered some alkylaromatic compoundsthat serve as surprisingly useful blend partners with conventional LABor LAS compositions, even though one would typically think such blendpartners would negatively impact surfactant performance. Accordingly, inyet further aspects, the present invention relates to blends betweenhydrocarbon mixtures (and/or sulfonates thereof) and LAB and/or LAScompositions. Such hydrocarbon mixtures according to some embodimentsmay be treated or untreated (e.g., may or may not be subjected toextractions), and may further be highly purified in one or two types ofcompound (e.g., di-alkylbenzenes and/or alkylated naphthalenes), and maybe obtained through separation from a crude fraction or otherhydrocarbon mixture, but may also advantageously be obtained byalkylation, or any other means for obtaining such highly purifiedcompounds. These alternatives to conventional LAB and/or LAScompositions may provide substantial advantages to surfactantformulations, including more economical production and/or enhancedsurfactant properties such as critical micelle concentration (CMC),wetting, foaming, and the like.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of a process and system for treatinghydrocarbon mixtures and sulfonation that may be employed in accordancewith some embodiments.

FIG. 2 is a schematic diagram of one alternative process and system fortreating hydrocarbon mixtures and sulfonation that may be employed inaccordance with other embodiments.

FIG. 3 is an illustration of a reaction process that may be suitable forsulfonation in accordance with some embodiments.

FIG. 4 is an illustration of another reaction process that may besuitable for sulfonation in accordance with other embodiments.

FIG. 5 is a graph of surface tension (mN/m) vs. sulfonated sampleconcentration in water (wt %) used to determine CMC values for samplesin connection with Example 2.

FIG. 6 is a graph of the volume of 1% CaCl₂ solution added to samplesolutions in accordance with Example 2 vs. Haze No., used to determineCa tolerance in connection with Example 2.

FIG. 7 is a graph of surface tension (mN/m) vs. sulfonated sampleconcentration in water (wt %) used to determine CMC values for samplesin connection with Example 2.

FIG. 8 is a graph of the volume of 1% CaCl₂ solution added to samplesolutions in accordance with Example 2 vs. Haze No., used to determineCa tolerance in connection with Example 2.

FIG. 9 is a graph of surface tension (mN/m) vs. sulfonated sampleconcentration in water (wt %) used to determine CMC values for samplesin connection with Example 2.

FIG. 10 is a graph of the volume of 1% CaCl₂ solution added to samplesolutions in accordance with Example 2 vs. Haze No., used to determineCa tolerance in connection with Example 2.

FIG. 11 is a graph of surface tension (mN/m) vs. sulfonated sampleconcentration in water (wt %) used to determine CMC values for samplesin connection with Example 2.

FIG. 12 is a graph of the volume of 1% CaCl₂ solution added to samplesolutions in accordance with Example 2 vs. Haze No., used to determineCa tolerance in connection with Example 2.

FIG. 13 is a graph showing CMC ranges measured for various blendcompositions in connection with Example 4.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, “wt %” means percentage by weight, “vol %” meanspercentage by volume, “mol %” means percentage by mole, “ppm” meansparts per million, and “ppm wt” and “wppm” are used interchangeably tomean parts per million on a weight basis. All “ppm” as used herein areppm by weight unless specified otherwise. All concentrations herein areexpressed on the basis of the total amount of the composition inquestion. Thus, the concentrations of the various components of thefirst mixture are expressed based on the total weight of the firstmixture. All ranges expressed herein should include both end points astwo specific embodiments unless specified or indicated to the contrary.

Nomenclature of elements and groups thereof used herein are pursuant tothe Periodic Table used by the International Union of Pure and AppliedChemistry after 1988. An example of the Periodic Table is shown in theinner page of the front cover of Advanced Inorganic Chemistry, 6^(th)Edition, by F. Albert Cotton et al. (John Wiley & Sons, Inc., 1999).

As used herein, a “carbon number” refers to the number of carbon atomsin a compound. Likewise, a “C_(x)” compound is one having x carbon atoms(i.e., carbon number of x), and a “C_(x)-C_(y)” or “C_(x-y)” compound isone having from x to y carbon atoms.

An “alkyl” group or moiety, unless otherwise noted, includes branched,unbranched, cyclic, and acyclic saturated hydrocarbon moieties. A“substituted” hydrocarbon is a hydrocarbon (or hydrocarbon moiety) inwhich at least one H is replaced with another moiety. For instance, analkyl-substituted benzene is a benzene with one or more alkyl moietiessubstituted for one or more pendent H atoms of the benzene.

Various embodiments described herein provide processes for obtaining,and compositions comprising, alkylaromatic sulfonates. These processesadvantageously may use crude fractions or other hydrocarbon mixtures asstarting material; the hydrocarbon mixture may be treated to tailor itscomposition, particularly with respect to alkyl aromatic compounds inthe hydrocarbon mixture, thereby forming an alkylaromatic precursorcomposition, which is then sulfonated. Surprisingly, it has been foundthat many of the resulting sulfonated alkylaromatic compositions exhibitacceptable or even in some cases superior surfactant properties, ascompared to the modern conventional alkylaromatic sulfonates, which areformed by alkylating benzene to obtain compositions having a narrowmolecular distribution of only a few isomers of particular mono-linearalkyl benzenes. The compositions of many embodiments of the presentinvention (and/or those obtained through processes in accordance withvarious embodiments herein) exhibit broader molecular distribution, butstill achieve excellent surfactant performance when such diversecompositions are formulated. Furthermore, targeted treatments and othermeans of tailoring the composition of various hydrocarbon compounds thatare subjected to sulfonation according to various embodiments providesurprising performance gains over previously investigated petroleumsulfonates. Many of the aforementioned processes and compositions aredescribed in further detail below, and many more embodiments will beapparent to the skilled artisan upon reading the following description.

Obtaining a Hydrocarbon Mixture

Hydrocarbon mixtures for use in various embodiments of the presentinvention comprise (or consist essentially of) C₇-C₃₀ hydrocarbons,preferably C₁₆-C₂₈ hydrocarbons, such as C₁₆-C₂₁ hydrocarbons. In yetother embodiments, the hydrocarbon mixture may comprise (or consistessentially of) C₇ to C₁₇ hydrocarbons (useful, e.g., for alkylaromaticsulfonates intended for hydrotrope applications). In yet furtherembodiments, the hydrocarbon mixture may comprise (or consistessentially of) a broader range of C₇ to C₆₀ hydrocarbons (providingalkylaromatics suitable for, e.g., EOR applications). In any of theforegoing embodiments, at least 90 wt %, preferably at least 95 wt %,more preferably at least 99 wt %, of the hydrocarbon mixture is composedof hydrocarbons having any of the aforementioned C_(x)-C_(y) ranges(i.e., any of the aforementioned numbers of carbon atoms).

According to certain embodiments, the hydrocarbon mixture can be furthertailored to suit desired needs of an end product alkylaromaticsulfonate. For instance, a hydrocarbon mixture comprising at least 90,95, or even 99 wt % C₁₆-C₂₁ hydrocarbons may be particularly well-suitedto obtaining an alkylaromatic sulfonate composition with low-foamingproperties, which are preferred for use as a hydrotrope component in adetergent formulation. On the other hand, a hydrocarbon mixturecomprising at least 90, 95, or even 99 wt % C₂₂-C₂₆ hydrocarbons may bewell-suited to obtain alkylaromatic sulfonate compositions with criticalmicelle concentration (CMC) comparable to conventional LAS compositionsformed from a process using alkylation of benzenes; such alkylaromaticsulfonate compositions may accordingly be useful as the activesurfactant in detergent for cleaning or soaping applications. They mayalso be employed as lubricating oil surfactants, and/or as components inEOR applications, drilling fluids, and other oilfield applications.

Hydrocarbon mixtures of various embodiments may be obtained from avariety of sources. One preferred source is a crude oil mixture, fromwhich various distillation cuts may be obtained. Thus, processes of someembodiments include obtaining the hydrocarbon mixture as a crude oilfraction. In particular of these embodiments, the hydrocarbon mixturecan be alternatively (or additionally) characterized in terms of theboiling point ranges of the constituents of the crude oil fraction. Forinstance, a hydrocarbon mixture according to some embodiments is a crudeoil fraction having boiling point range from 140° C. to 420° C. Incertain of these embodiments, such a fraction may be characterized ascomprising at least 90, 95, or even 99 wt % C₁₂-C₂₆ hydrocarbons.

A crude fraction according to such embodiments may be obtained by anysuitable separation means known in the art, such as distillation,flashing, or the like.

In particular embodiments (whether the hydrocarbon mixture ischaracterized by carbon numbers, boiling point range, or both), thehydrocarbon mixture comprises 5-40 wt %, preferably 10-40 wt %, such as15-35 wt %, or 20-40 wt %, sulfonatable aromatics, with ranges from anyof the foregoing low values to any of the foregoing high values alsocontemplated. The hydrocarbon mixture also comprises 60-95 wt %,preferably 60-90 wt %, such as 65-85 wt %, or 60-80 wt %, compoundsother than sulfonatable aromatics (e.g., saturated hydrocarbons such asbranched and unbranched alkyl, cycloalkyl, and the like; and alsoincluding non-aromatic olefins) and heteroatom-containing compounds(e.g., S-containing and/or N-containing compounds).

Sulfonatable aromatics include single-ring and multi-ringalkylaromatics. Although the initial hydrocarbon mixture may containnon-aromatic olefins, which could technically be sulfonated, inpreferred embodiments, such olefins, if present in the hydrocarbonmixture, are removed by treatment (e.g., by hydrotreatment, described inmore detail below). Thus, references herein to “compounds other thansulfonatable aromatics” should be taken to include any olefins otherthan the foregoing aromatics that may be present in the hydrocarbonmixture before or after treatment. In some embodiments, the 5-40 wt %,10-30 wt %, or 15-25 wt % sulfonatable aromatics of the hydrocarbonmixture are selected from the group consisting of mono-alkyl benzenes(1R alkylaromatics), multi-alkyl benzenes (1.5R alkylaromatics), 2+Ralkylaromatics (alkyl-substituted polycyclic aromatics), and anycombination of the foregoing. “1R alkylaromatics” or “mono-alkylbenzenes” are benzenes having one alkyl substitution thereon.“Multi-alkyl benzenes” as used herein reference benzenes having two ormore alkyl substitutions thereon (e.g., di-alkyl, tri-alkyl, tetra-alkylbenzenes, and the like), and optionally include benzenes in which anytwo adjacent alkyl substitutions are joined to form a non-aromatic ringfused to the benzene, provided that either the benzene or the fusednon-aromatic ring is further alkyl-substituted. Examples of the lattertype of compounds include, e.g., mono- or poly-alkyl substitutedtetralin (with alkyl substitutions on either or both the benzyl orcyclohexyl ring of the tetralin base structure). Multi-alkyl benzenesmay be referred to herein by the shorthand “1.5R alkylaromatics.”“Polycyclic aromatics,” sometimes referred to herein by the shorthand“2+R alkylaromatics,” are polycyclic aromatic hydrocarbons having one ormore alkyl substitutions, meaning compounds having 2 or more aromaticrings fused together (with 1 or more alkyl substitutions on any one ormore of the aromatic rings). These include alkyl-substituted naphthenes(a 2-ring alkylaromatic), substituted anthracenes (3-ringalkylaromatics), and the like, where the alkyl substitution(s) may be onany one or more of the aromatic rings.

Suitable mono-alkylbenzenes (1R alkylaromatics) include those havingstructure according to one of Formulas (I) and (II) below:

In each of Formula (I) and (II), R¹ is C₁-C₁₅ alkyl, preferably C₁-C₁₂alkyl, for instance C₁-C₈ alkyl. R¹ may be branched, but preferably itis either not branched or has branching such that pendent chains (i.e.,carbon chains not part of the main, or longest, chain of the moiety) areno longer than 2 carbon atoms. R² in Formula (II) is C₁-C₈ alkyl,preferably C₁-C₅ alkyl. As with IV, R² may be branched, but preferablyit is either not branched or has branching such that pendent chains(i.e., non-main carbon chains) containing no more than 2 carbon atoms.

As noted, the sulfonatable aromatics of the hydrocarbon mixture may alsocomprise 1.5R alkylaromatic compounds. Such compounds include (i)poly-alkylbenzenes (preferably di- and/or tri-alkylbenzenes) and (ii)alkyl-substituted tetralins.

Di-alkylbenzenes are particularly suitable 1.5R alkylaromatics accordingto some embodiments. Di-alkylbenzenes of such embodiments include thosehaving structure according to one of Formulas (III), (IV), and (V)below:

In Formulas (III)-(V), R¹ is as defined in Formulas (I) and (II),provided that the total number of carbon atoms in each formula does notexceed 60 (preferably not to exceed 30, 26, 21, or even 17 in someembodiments). R³ also has the same definitions as R¹, although R¹ and R³may be the same or different. Particular examples of di-alkylbenzenesinclude 1-dodecyl-4-methylbenzene (i.e., a structure according toFormula (V) in which R³ is C₁₀ dodecyl, and R¹ is a methyl group);1,4-dioctylbenzene (Formula (V) in which both R¹ and R³ are C₈unbranched alkyl).

Similarly, suitable tri-alkylbenzenes include three alkyl substitutionsat any three of the carbons along the benzene ring, where each alkylsubstitution may be in accordance with the R¹ and/or R³ groups discussedabove with respect to formulas (III), (IV), and (V), provided that eachalkyl group may be the same or different with respect to the other twoalkyl groups. For instance, an example of a suitable tri-alkylbenzene ismesitylene (in which the three alkyl substitutions are located onalternating carbons of the benzene ring, and each of the three alkylsubstitutions is a methyl, or C₁, substitution).

1.5R alkylaromatics of some embodiments also or instead includetetralins (also known as 1,2,3,4-tetrahydronaphthalenes) having 1, 2, 3,or 4 alkyl substitutions at any one or more hydrogens on the tetralinmoiety. Preferably, the alkyl-substituted tetralins contain 0, 1, or 2alkyl substitutions on each of the benzyl ring and the cyclohexyl ringof the tetralin, for instance as shown below in Formula (VI):

In Formula (VI), R⁴, R⁵, R⁶, and R⁷ are each independently selected inaccordance with R¹ as discussed with respect to Formulas (I) and (II),provided that the total number of carbons in Formula (VI) does notexceed 60 (preferably 30, 26, 21, or even 17 in some embodiments).

Some particularly useful examples according to yet other embodimentsinclude mono-alkyl tetralins, such as 6-butyl-tetralin (also known as6-butyl-1,2,3,4-tetrahydronaphthalene). In general, suitable mono-alkyltetralins may have a C₁-C₁₅ (preferably C₁-C₁₂, such as C₁-C₈) alkylgroup substituted at any point on the tetralin. Such alkyl group may bebranched, but it is preferably unbranched, or, where branched, pendentchains are no longer than 2 carbon atoms.

Other useful examples of 1.5R alkylaromatic compounds include thosehaving 2 alkyl substitutions in the para-positions on the cyclohexylring of the tetralin moiety, i.e., compounds in accordance with Formula(VII) below:

In Formula (VII), R⁸ and R9³ may be the same or different, and are eachin accordance with IV and R³ as described with respect to Formulas(III)-(V), provided that the total number of carbon atoms in Formula(VII) does not exceed 60 (preferably not to exceed 30, 26, or even 21 insome embodiments). Examples include 1-decyl-4-methyl-tetralin (i.e.,compounds according to Formula (VII) where R⁸ is decyl and R⁹ ismethyl).

In yet further embodiments, 1.5R alkylaromatics may have 2 alkylsubstitutions according to R⁸ and R⁹, respectively, at any hydrogenalong the benzene and/or along the cyclohexane ring of the compound.That is, the 1.5R alkylaromatics according to such embodiments includestructural isomers of compounds according to Formula (VII) in which thetetralin core is retained, but the location(s) of the pendent alkylgroups may be moved.

Sulfonatable aromatics of hydrocarbon mixtures may further comprise 2+Ralkylaromatic compounds, i.e., those having 2 or more fused rings andone or more alkyl substitutions. These compounds includealkyl-substituted naphthalenes and anthracenes, particularly thosehaving 1, 2, 3, 4, 5, or 6 alkyl substitutions (preferably from 1 to 4alkyl substitutions), with each alkyl substitution independentlyselected from C₁-C₁₅ alkyl, provided that total number of carbons in thecompound does not exceed 60 (preferably not to exceed 30, 26, 21, oreven 17 in some embodiments). The alkyl substitutions are eachpreferably unbranched. Where the alkyl substitution is branched, pendentbranches preferably contain no more than 2 carbon atoms.

2+R alkylaromatics of some embodiments are preferably alkyl-substitutednaphthalenes. In some embodiments, the alkyl substituted naphthalenesare mono-, di-, tri- or tetra-alkyl substituted naphthalenes, i.e., theyhave structure in accordance with Formula (VIII) below:

In Formula (VIII), each of R¹⁰, R¹¹, and R¹² is independently selectedfrom H and C₁-C₁₅ alkyl, preferably C₁-C₁₂ alkyl, for instance C₁-C₈alkyl, provided that the total number of carbon atoms in Formula (VIII)does not exceed 60 (preferably 30, or in some embodiments 26, 21, oreven 17). Furthermore, each of R¹⁰-R¹² may be branched, but preferablyeach is either not branched or has branching such that pendent chainscontain no more than 2 carbon atoms. For mono-alkyl-substitutednaphthalenes, 2 of R¹⁰, R¹¹, and R¹² are H; for di-alkyl-substitutednaphthalenes, only 1 of R¹⁰, R¹¹, and R¹² is H; and fortri-alkyl-substituted naphthalenes, none of R¹⁰, R¹¹, and R¹² are H.

In yet other embodiments, each benzyl ring in an alkyl-substitutednaphthalene has 0, 1, or 2 alkyl substitutions, as shown in Figure (IX)below, where R¹³, R¹⁴, R¹⁵, and R¹⁶ are each independently selected inaccordance with R¹ of Formula (I):

In some particular embodiments, the mono-, di-, and/ortri-alkyl-substituted naphthalenes are such that R¹¹ and R¹² are each Hor C₁-C₃ alkyl, and R¹⁰ is C₄-C₁₂ (preferably C₄-C₁₀) alkyl. In suchembodiments, each R group is preferably unbranched, or where branched,with pendent chains containing no more than 2 carbon atoms. Forinstance, then, R¹¹ and R¹² are each C₁-C₃ alkyl to provide atri-alkyl-substituted naphthalene according to such embodiments. Oneparticular example of a tri-alkyl substituted naphthalene according tosuch embodiments includes 6,7,-dimethyl-1-(4-methylpentyl)-Naphthalene(i.e., Formula (VIII) where R¹¹ and R¹² are each methyl, and R¹⁰ ismethylpentyl).

In some embodiments, particularly (but not necessarily) those in whichthe hydrocarbon mixture is obtained from a crude fraction, thesulfonatable portion of the hydrocarbon mixture may exhibit a broadmolecular distribution. For instance, the sulfonatable aromatics of thehydrocarbon mixture of such embodiments preferably comprises at least 1Rand 1.5R alkylaromatics, and more preferably also comprises 2+Ralkylaromatics. The sulfonatable aromatics of the hydrocarbon mixturesof some such embodiments may comprise 35-75 wt % 1R alkylaromatics, 5-75wt % 1.5R alkylaromatics, and 0-50 wt % 2+R alkylaromatics, providedthat the total of all three does not exceed 100 wt % (such wt % s basedupon the mass of sulfonatable aromatics in the hydrocarbon mixture).

Alternatively, according to yet other embodiments, the hydrocarbonmixture may be characterized as comprising 1.75-30 wt % (such as3.5-22.5 wt %, or 5.25-26.25 wt %) 1R alkylaromatics; 0.25-30 wt % (suchas 0.5-22.5 wt %, or 0.75-26.25 wt %) 1.5R alkylaromatics; and 0-20 wt %(such as 1-15 wt % or 5-17.5 wt %) 2+R alkylaromatics, such wt % s basedon the total mass of the hydrocarbon mixture. Ranges from any of theforegoing low ends to any of the foregoing high ends for each of the 1R,1.5R, and 2+R alkylaromatics are also contemplated in some embodiments.

In yet other embodiments, the hydrocarbon mixture may be obtained in amanner such that the mixture comprises a substantial majority and/orsubstantially entirely a desired compound according to the foregoingcompounds. Hydrocarbon mixtures according to such embodiments may beparticularly useful for blending with LAB or LAS compositions, whichwill be discussed in more detail below. For instance, a hydrocarbonmixture according to some embodiments may comprise predominantly onlyone of the types of alkylaromatics (e.g., it may comprise 60-100 wt %,such as 75-95 wt %, or 90-100 wt % of one of the following: 1Ralkylaromatics, 1.5R alkylaromatics, or 2+R alkylaromatics, wherein eachclass of alkylaromatic may contain compounds in accordance with theforegoing descriptions of each). In some embodiments, such hydrocarbonmixtures may consist essentially of the 1R alkylaromatics, 1.5Ralkylaromatics, or 2+R alkylaromatics, meaning that only minor amounts(e.g., less than 100 ppm) of sulfonatable aromatics other than theforegoing are present in the hydrocarbon mixture of such embodiments.One or more such hydrocarbon mixtures may thereafter be blended with aLAB compound and sulfonated; or, sulfonated and then blended with a LAScompound, to form a blended alkylaromatic sulfonate composition. Asnoted, such blending is later described in more detail herein.

Treating the Hydrocarbon Mixture to Obtain a Precursor AlkylaromaticComposition

Processes of various embodiments include treating the hydrocarbonmixture, thereby obtaining a precursor alkylaromatic composition withcomposition tailored for sulfonation. Treatment may include any one ormore of various processes known in the art for concentrating a crude oilfraction in sulfonatable aromatics, especially alkylaromatics. A widevariety of treatments are known in the art: for instance, hydrotreatingcan be used to remove various impurities from a crude oil fraction, suchas heteroatom (S- and N-containing) compounds (see, for instance, U.S.Pat. Nos. 3,957,627 and 4,224,144). Other exemplary treatments includesolvent extraction to remove separate species of varying solubilities ina given solvent (i.e., relatively more or less polar species). A widevariety of solvents may be used in solvent extraction, targetingcompounds of various solubilities; in particular embodiments, extractionis carried out with one or more solvents useful for increasing theconcentration of aromatic compounds in a hydrocarbon composition. Othertreatment options include catalytic reforming and dehydrogenation, e.g.,to convert alkanes into aromatics (see, for instance, U.S. Pat. Nos.2,915,455; 5,011,805; 5,885,439; and 6,773,580).

Processes according to various embodiments include treating thehydrocarbon mixture to arrive at a desired mixture of components. Forinstance, some embodiments include treating the hydrocarbon mixture soas to obtain a precursor alkylaromatic composition comprisingsulfonatable aromatics at a wt % greater than the wt % of sulfonatablearomatics in the untreated hydrocarbon mixture. For instance, aprecursor alkylaromatic composition, following treatment, may comprisesulfonatable aromatics within the range from a low of 30, 35, 40, 45,50, 55, or 60 wt %, to a high of 62, 65, 75, 80, 85, 90, or 95 wt %. Insome preferred embodiments, the precursor alkylaromatic compoundcomprises an even higher wt % of sulfonatable aromatics (e.g., rangingfrom a low of 75, 80, or 85 wt % to a high of 85, 90, 95, or even 99 wt%, provided the high end of the range is greater than the low end).

Solvent extractions that increase the wt % of aromatic compounds (and/ordecrease the wt % of other compounds, such as saturated compounds) areparticularly useful for increasing the wt % of sulfonatable aromatics.In particular embodiments, treatment includes subjecting the hydrocarbonmixture to 1, 2, 3, 4, or 5 such solvent extractions, thereby increasingthe wt % of sulfonatable aromatics in the precursor alkylaromaticcomposition relative to the untreated hydrocarbon mixture. Solventextractions that increase aromatic content in a hydrocarbon compositioninclude, but are not limited to, N-methyl-2-pyrrolidone (NMP)extraction, sulfolane extraction, furfural extraction, and/or extractionusing dimethyl sulfoxide (DMSO), sulfur dioxide (SO2), sulfuric acid,and/or phenol. Also or instead, such solvent extractions can be carriedout so as to tailor aromatics (e.g., increase the relative amount of 1R,1.5R, or 2+R alkylaromatics) in the composition, and/or to reduceoverall aromaticity. For instance, in some instances, a mild NMPextraction may be used to remove 2+R alkylaromatics prior to extractingthe obtained raffinate more severely to obtain the 1R and 1.5Ralkylaromatics. Methods for carrying out such extractions are well knownin the art. See, for instance, U.S. Pat. Nos. 2,079,885; 2,698,276;3,338,823; 3,544,453; 3,556,991; 3,567,627; 3,723,256; 3,929,616;4,013,549; 4,053,369; 4,571,295; 4,909,927; 5,041,206; 6,866,772; and7,078,580; see also US Patent Publication No. 2016/0075954; and F. Lee,et al., “Two Liquid-Phase Extractive Distillation for AromaticsRecovery,” Ind. Eng. Chem. Res. (26) No. 3, pp. 564-573, (1987).Suitable solvent extractions for increasing the aromatic content of ahydrocarbon mixture will be readily apparent to the skilled artisan inview of the present disclosure. In some particular embodiments, NMPextraction may be preferred. Advantages of NMP extraction include higherselectivity for desired molecules, less toxic solvent, and relativelyeasier recovery of the solvent from the oil.

In general, the greater the number of solvent extractions, the higherthe wt % of aromatics (and therefore higher wt % of sulfonatablearomatics) in the precursor alkylaromatic composition. For instance, anuntreated hydrocarbon mixture of some embodiments may comprise 15-25 wt% sulfonatable aromatics. Treatment according to such embodimentsincluding one or more NMP extractions may yield a precursoralkylaromatic composition comprising: 35-50 wt % sulfonatable aromatics(1 extraction); 45-55 wt % sulfonatable aromatics (2 extractions); 55-75wt % sulfonatable aromatics (3 extractions); and 65-85 wt % sulfonatablearomatics (4 extractions).

However, while increasing number of extractions increases the wt % ofsulfonatable aromatics in the precursor alkylaromatic composition, italso reduces the overall yield of the hydrocarbon feed provided tosulfonation. Further, greater number of extractions means greaterexpense and complexity of the system. It is therefore desired to find abalance; hence, 1, 2, or 3 extractions are preferred in certainembodiments.

Extraction according to particular embodiments employs not only aparticular solvent, but also extraction conditions suitable to obtain adesired molecular distribution among the sulfonatable aromatics. Forinstance, NMP extraction can be carried out at mild, moderate, or severeconditions. Mild, moderate, or severe conditions refer to the yield ofthe extract phase. Lower extract yields, for example less than 10 vol %of feed, are obtained under mild conditions. Higher extract yields, forexample greater than 10 vol % of feed, are obtained at more severeconditions. Any combination of conditions such as solvent treat ratio,water content in solvent, and extractor temperature can be used toincrease or decrease the amount of molecules which partition into theextract phase to adjust the severity between mild, moderate, and severe.In general, increasing treat rate, increasing temperature, anddecreasing water content will each increase the severity of theextraction.

Depending on the solvent selected and extraction severity, a differentdistribution among 1R, 1.5R, and 2+R alkylaromatics may be obtainedwithin the sulfonatable aromatics of the precursor alkylaromaticcomposition. For instance, mild NMP extraction may yield a raffinateprecursor alkylaromatic composition having fewer 2+R alkylaromaticsrelative to 1R and 1.5R alkylaromatics, while severe NMP extraction ofthe raffinate may result in greater relative removal of 1Ralkylaromatics. Although many possibilities exist for adjusting relativeconcentration of 1R, 1.5R, and 2+R alkylaromatics using variousextraction techniques, the following general guidance is noted:

-   -   Extractions (solvent/conditions) to decrease 1R relative wt %:        ≧100% treat rate (the amount of solvent, in vol %, used relative        to the volume of hydrocarbon feed; greater than 100% means to        employ a greater volume (or volumetric feed rate) of solvent        than feed for the treatment); ≦1 wt % water in solvent;        temperature ≧25° C.;    -   Extractions (solvent/conditions) to decrease 1.5R relative wt %:        ≧100% treat rate; ≦1 wt % water in solvent; temperature ≧25° C.;    -   Extractions (solvent/conditions) to decrease 2+R relative wt %:        ≦100% treat rate; ≦1 wt % water in solvent; temperature ≦25° C.

According to some embodiments, other treatment methods may be employed,alone or in combination with extraction. For instance, hydrotreating maybe employed prior to, between, or after, any one or more of the 0, 1, 2,3, 4, or 5 extractions so as to remove heteroatoms (especially N- andS-containing compounds). Preferably, hydrotreatment is carried out priorto the 0, 1, 2, 3, 4, or 5 extractions. Also, the hydrotreatment ispreferably carried out using relatively low temperature (300° C. orless) and/or high pressure (200 psig or greater) with a catalyst havingmetals sites.

Some processes also or instead include reforming and dehydrogenation toconvert a fraction of alkanes (e.g., in particular to convertcycloalkanes and/or isoparaffins) in the hydrocarbon mixture toaromatics (especially alkylaromatics). In certain embodiments, one ormore extraction effluent streams rich in saturated hydrocarbons (e.g.,hydrocarbons separated from the hydrocarbon mixture using any one ormore extractions) may be catalytically reformed and dehydrogenated so asto convert at least a portion of the saturates (especially cycloalkanesand/or isoparaffins) to aromatics (especially alkylaromatics). Anysuitable reforming/dehydrogenation process may be employed, although insome particular embodiments, mild reforming (350° C.-400° C., <400 psig,1-2 hr⁻¹ LHSV, Re/Pt catalyst) may be utilized. Preferably, wherereforming is used in combination with extraction, the reformate productis supplied to one or more solvent extractions (e.g., by recycling orpassing to a downstream extraction).

It should further be noted that any of various treatments may beintermingled with one or more distillation steps (e.g., one or moredistillation steps used to obtain the hydrocarbon fraction),particularly where processes in accordance with some embodiments areintegrated into existing refinery operations. For instance, a firstdistillation may be followed by a first hydrotreatment, in turn followedby a second distillation, before the hydrocarbon mixture (containing amixture of hydrocarbons in accordance with the above descriptions) isobtained. Thus, unless specifically noted otherwise, it should beunderstood that there may be some degree of commingling between (i)processes in connection with obtaining the hydrocarbon mixture ofvarious embodiments, and (ii) treatment processes of variousembodiments. Nonetheless, in particular embodiments, one or moredistillations may be carried out before and/or after one or morehydrotreatments; any extractions employed as part of treatment are thencarried out following all distillations and hydrotreatments.

FIG. 1 provides one example of a treatment process that may be employedin accordance with various embodiments. In FIG. 1, a hydrocarbon mixture102 is obtained as a crude fraction following distillation 101. Thehydrocarbon mixture 102 is passed to hydrotreatment 105 to provide ahydrotreated stream 106, which is passed to distillation 107. Analkylbenzene fraction 108 is obtained and passed to a first solventextraction 110. According to the process shown in FIG. 1, first solventextraction 110 is carried out using NMP at mild conditions (66% treatrate, 0.5 wt % H₂O in solvent, 25° C.). The first solvent extraction 110serves to remove 2+R alkylaromatics in effluent 111, leaving anintermediate hydrocarbon stream 115 concentrated in 1R and 1.5Ralkylaromatics, which is in turn provided to second solvent extraction120. The second solvent extraction 120 as shown in FIG. 1 is operated atsevere conditions (e.g., 225% treat rate, 0.5 wt % H₂O in solvent, 25°C.) to provide a second extraction product 125 further concentrated inaromatics (in particular 1R and 1.5R alkylaromatics), with an effluent121 rich in saturated hydrocarbons drawn off. The second extractionproduct 125 is provided as the precursor alkylaromatic composition tosulfonation 130, from which the alkylaromatic sulfonate product 135 isproduced. An oil-rich phase 131 is withdrawn from sulfonation, asdescribed in more detail below.

FIG. 2 illustrates two modifications of the process shown in FIG. 1, inaccordance with yet other embodiments. First, the effluent 121 rich insaturated hydrocarbons is provided to a reforming system 210 in which atleast a portion of the saturated hydrocarbons of the effluent 121 areconverted to aromatics, from which is obtained an aromatic-concentratedrecycle 215 to be provided to the first solvent extraction 110. Second,the second extraction product 125 is subjected to one or more additionalextractions 250, in which the product 125 is further concentrated inaromatics (particularly 1R alkylaromatics) following removal of one ormore effluents 251 rich in saturated hydrocarbons, thereby providing afurther treated product 225 which is sent to sulfonation 130 as thetreated hydrocarbon stream.

Further guidance in targeting particular types of aromatic compound forretention and/or removal from the precursor alkylaromatic composition isprovided in the Examples section below. Other methods for targetingparticular types of aromatic compounds will be apparent to theordinarily skilled artisan in view of the teachings of the presentdisclosure.

Treatment with solvent extraction according to some embodiments mayfurther include, following any one or more extractions, distillation orother separation so as to remove the solvent(s) from the treatedhydrocarbon. For example, in a solvent recovery tower, water can beadded to raffinate or extract phases at temperatures between 25° C. and90° C. The oil will separate from the water/solvent and form a light topphase. The product oil can be collected by siphoning from the top of thesolvent recovery tower. The bottom heavy phase (water/solvent) can becollected by siphoning from the bottom of the solvent recovery tower. Torecover the solvent, one may bring the water/solvent to >90° C. (suchas >100° C.) in order to boil off the water.

Accordingly, in general, the hydrocarbon mixture of some embodiments issubjected to one or more treatments such that the precursoralkylaromatic composition comprises 0-40 wt %, such as 5-40 wt %(preferably 0-20 or 0-25 wt %, such as 10-20 or 10-25 wt %) 2+Ralkylaromatic compounds; 10-45 wt % (preferably 15-30 wt %) 1.5Ralkylaromatic compounds; and 15-50 wt % (preferably 15-35, such as 10-25wt %) 1R alkylaromatic compounds, said wt % s determined on the basis ofthe precursor alkylaromatic composition. Ranges from any of theaforementioned low ends to any of the aforementioned high ends are alsocontemplated for each of the 2+R, 1.5R, and 1R alkylaromatics.Furthermore, in each of the aforementioned embodiments, any one or more,and preferably each, of the 1R, 1.5R, and 2+R alkylaromatics is presentin the precursor alkylaromatic composition at a wt % greater than eachsuch compound was present in the hydrocarbon mixture (i.e., prior to theone or more treatments). Further, the precursor alkylaromaticcomposition may have a broad molecular distribution among the 1R, 1.5R,and 2+R alkylaromatic compounds, meaning that the wt % s of each of the1R, 1.5R, and 2+R alkylaromatic compounds in the precursor alkylaromaticcomposition are similar to each other. For instance, in someembodiments, the wt % of the 1.5R alkylaromatics in the precursoralkylaromatic composition (1) differs from the wt % of the 1Ralkylaromatics in the precursor alkylaromatic composition by no morethan 10 wt %, and (2) differs from the wt % of the 2+R alkylaromatics inthe precursor alkylaromatic composition by no more than 10 wt %.

Other, more particular, molecular distributions may be targeted invarious embodiments; in some of these embodiments, a differentapplication of the sulfonated product of the precursor alkylaromaticcomposition may be contemplated, depending upon the moleculardistribution. Some sample distributions, and potential applicationsaccording to some such embodiments, are summarized in Table 1 below.

Sulfonation

The precursor alkylaromatic composition according to various embodimentsmay be subjected to sulfonation in order to obtain an alkylaromaticsulfonate composition.

Sulfonation may be carried out by any suitable process known in the artfor sulfonating aromatic compounds so as to substitute a sulfonate groupfor a hydrogen atom on the aromatic ring of such compound. For instance,sulfonation may conveniently be carried out according to conventionalsulfonation methods utilized for commercial linear alkyl benzene (LAB)compositions. Such methods include contacting the precursoralkylaromatic composition with a sulfonating agent such as sulfuric acidor a sulfur trioxide compound. Suitable sulfur trioxide compoundsinclude oleum, otherwise known as fuming sulfuric acid, which comprisessulfur trioxide (typically 10-25%) in sulfuric acid; other suitablesulfur trioxide compounds include an SO³-air mixture. Reaction betweenthe precursor alkylaromatic composition and the sulfonating agentproduces an alkylaromatic sulfonic acid, in which an SO₃ moiety isappended to the aromatic ring (or, where multiple aromatic rings arepresent, any one or more of the aromatic rings may have an SO₃ moietyappended thereto).

The acid may exist as a cationic species or as the acid. Either way, thecomposition is neutralized using any of a variety of bases. Examples ofsuitable bases include sodium, potassium, calcium, magnesium, ammonia,amines (e.g., isopropylamine, methylamine, triethanolamine, etc.), andsalts thereof. For instance, aqueous NaOH, KOH, Ca(OH)₂ or the like maybe used for neutralization of the alkylaromatic sulfonic acid. Theresult is a composition comprising the alkylaromatic sulfonate and/orsalts thereof. That is, since the alkylaromatic sulfonate contains asulfonate moiety, it is anionic and therefore ionically bonds to theneutralization salt (e.g., Na). References herein to an “alkylaromaticsulfonate” are therefore intended to include both the anionic sulfonatespecies and its neutral salt (e.g., sodium salt, potassium salt,ammonium salt, or the like). Indeed, when used in applications such ashousehold detergents, industrial detergents, EOR applications, and thelike, the alkylaromatic sulfonate will likely exist in its neutral saltform.

Following neutralization, the composition may be purified (e.g., removalof saturated sulfate salt solution, such as Na₂SO₄ where sodium saltsare used for neutralization; as well as filtration, centrifuging,washing, drying, and/or other methods for removing the solid sulfonateproduct from aqueous solution).

FIG. 3 is an illustration of an example synthetic route for sulfonationof precursor alkylaromatic compositions according to some embodiments.Such a process is particularly useful for mixtures of 1R alkylaromaticcompounds. This process may be particularly suited for batchsulfonation, although it may be adapted to continuous sulfonation ifdesired (for instance, SO₃ in air may be used for continuoussulfonation). Per FIG. 3, precursor alkylaromatic composition 301 maycomprise a mixture of 1R, 1.5R, and 2+R alkylaromatics (withnon-limiting examples of such compounds illustrated in FIG. 3, and with1R alkylaromatics preferred). These are contacted with oleum to form thesulfonic acid 305, then neutralized with dilute NaOH. Saturated Na₂SO₄solution is removed, leaving the salt of the alkylaromatic sulfonate310. The salt is purified by stirring with water, centrifuging, andfiltering to remove the water wash. The washed solids 315 are furtherdried (e.g., at 75° C.) to obtain the alkylaromatic sulfonate product.

In yet other embodiments, the sulfonation process may be modified toaccount for differences that may exist between more typical commercialLABs and precursor alkylaromatic compositions in accordance with someembodiments (e.g., the presence of 1.5R and 2+R alkylaromatics inaddition to 1R alkylaromatics). In particular, sulfonation according tosome embodiments may include (1) removing an upper oil phase from thealkylaromatic sulfonic acid composition (e.g., by gravity separation)prior to or concurrent with neutralization (such oil phase comprisingfrom 10-60, such as 20-50, wt % of the sulfonic acid composition), and(2) modified purification to account for the fact that sulfonatedalkylaromatic salts according to some embodiments are water soluble.Thus, solvent extraction and separation from the solvent may bepreferred to remove the active sulfonated product from aqueous solution,rather than filtration and other solid/liquid separation techniques.Suitable sulfonation product solvents for this product extractioninclude isopropyl alcohol and other volatile solvents in which thesulfonates are soluble and sodium sulfonate is not.

Sulfonation processes according to such embodiments are illustrated inFIG. 4. Sulfonation in embodiments in accordance with FIG. 4 mayinclude: contacting the alkylaromatic precursor composition 401 withsulfonating agent (e.g., oleum, as shown in FIG. 4) to obtain thealkylaromatic sulfonic acid composition 405; separating an oil phasefrom the acid composition 405; and neutralizing the acid composition 405with base (e.g., aqueous NaOH, as shown in FIG. 4) to obtain a crudealkylaromatic sulfonate composition 410. Purification of the crudealkylaromatic sulfonate composition according to such embodiments mayinclude drying (e.g., filtration) to obtain a wet solid, and productextraction to obtain the alkylaromatic sulfonate composition (shown inFIG. 4 to be carried out using isopropyl alcohol (IPA) as a solvent).

Alkylaromatic Sulfonate Compositions

Alkylaromatic sulfonate compositions of some embodiments are preferablyobtained by processes according to any one or more of the foregoingembodiments. Alkylaromatic sulfonate compositions of various embodimentsmay comprise the sulfonate and/or sulfonate salt of any one or more ofthe previously described 1R, 1.5R, and 2+R alkylaromatic compounds (suchcompounds may also be referred to herein as 1R alkylaromatic sulfonates,1.5R alkylaromatic sulfonates, and/or 2+R alkylaromatic sulfonates,respectively). More particularly, alkylaromatic sulfonate compositionsmay comprise the sulfonate and/or sulfonate salt of any one or morecompositions in accordance with Formulas (I)-(VIII).

The alkylaromatic sulfonates of some such embodiments may beparticularly useful as surfactants, and in particular as detergents(e.g., in cleaning applications and/or for enhanced oil recoveryoperations), or as industrial detergents, enhanced oil recovery (EOR)applications, as demulsifiers, and the like.

Alkylaromatic sulfonates according to some embodiments have surfactantactivity within the range from 40 to 98%, such as within a range from alow of any one of 40, 50, 60, 70, and 75% to a high of any one of 70,75, 80, 85, 90, 95, and 98%, provided the high end of the range isgreater than the low end. As used herein with respect to alkylaromaticsulfonate compositions, “activity” or “surfactant activity” refers tothe percent of sulfonates in the composition, as determined according toASTM D3049. A sample of the composition is titrated with hyamine. Ingeneral, activity A=((V×N×EW)×100)/(W), where V is volume of hyamine(ml) needed to titrate the sample; N is the normality of hyamine titrant(meq/ml); EW is the equivalent weight of the sample (mg/meq); and W isthe weight (mass) of the sample (mg).

The alkylaromatic sulfonates of some embodiments may also or insteadexhibit any one or more of the following surfactant and/or detergentproperties:

-   -   Critical micelle concentration (CMC) within the range from        0.01-1.0 wt %, preferably within the range from 0.01-0.5 wt %,        more preferably within the range from 0.01-0.05 wt %. CMC is        determined in accordance with ISO 4311, utilizing the DuNouy        Ring method. Various serial dilutions of the product are made in        deionized water (starting with a 1% solution in deionized water,        diluted down until no measurable difference in surface tension        is detected compared to distilled water). Surface tensions are        plotted against the concentration. Surface tensions are measured        with a BZY Series Automatic Surface Tension meter using the Du        Nouy Ring method, which is based upon measuring the force        required to detach a platinum wire ring from a liquid surface or        from the interface between two liquids (in the case of        interfacial tension). See du Noüy, Pierre Lecomte, “An        Interfacial Tensiometer for Universal Use,” The Journal of        General Physiology, 7 (5): pp. 625-633 (1925). The region where        the curve shows no further decrease in surface tension with        increasing concentration is designated the CMC.    -   Draves wetting within the range from 100-600 sec; preferably        from 100-200 sec. Unless otherwise specified herein, Draves        wetting is determined in accordance with ASTM D2281-10.    -   Ross-Miles Foam height (initial) within the range from 10-75 mm        (initial), preferably within the range from 10-50 mm (initial),        more preferably within the range from 10-40 mm (initial), or        even 10-25 mm (initial). In terms of Ross-Miles Foam Height        (after 5 min): within the range from 10-55 mm, preferably within        the range from 10-50, more preferably within the range from        10-25 mm Unless otherwise specified herein, Ross-Miles foam        height is determined at initial time and after 5 min in        accordance with ASTM D1173-07.    -   Interfacial tension (IFT) of a 0.10 wt % solution of the        sulfonate in distilled water within the range from 5.5-9.5 mN/m;        preferably from 5.5-7.5 mN/m, more preferably from 5.5-7.0 mN/m.        Also or instead, such compositions may exhibit IFT of a 0.5 wt %        solution of the sulfonate in distilled water within the range        from 3.5-6.0, preferably 3.5-5.5 mN/m. IFT is determined using a        0.1 wt % solution of sample in distilled water. The interfacial        tension is measured against mineral oil in accordance with ASTM        D971, using a BZY Series Automatic Surface Tensionmeter        following the Du Nouy Ring Method (see description of CMC        measurements, above). The solution of sulfonate in water is        placed in a glass beaker and the platinum ring is then immersed        below the surface. Mineral oil is poured on top. The ring is        then raised through the solution:oil interface and the force        necessary to detach it from the bottom aqueous phase is        measured. Deionized water is used as the comparator aqueous        phase against which IFT values for the solutions are compared.    -   Calcium tolerance (which may otherwise be referred to as “hard        water tolerance”) within the range from 50-90 mg Ca/g sulfonate        (i.e., grams of the alkylaromatic sulfonate); preferably within        the range from 60-90 mg Ca/g sulfonate; more preferably within        the range from 65-90 mg Ca/g sulfonate. Unless specifically        noted otherwise herein, calcium tolerance is determined by        adding CaCl₂ to a sample of X grams of the alkylaromatic        sulfonate until a turbidity of 50 nephelometric turbidity units        (NTU) is obtained, as measured according to ISO 7027 using a        LaMotte 2020E turbidity meter (or equivalent suitable for ISO        7027 measurements). The amount of CaCl₂ (mg) necessary to obtain        the 50 NTU turbidity is recorded, and divided by the X grams of        alkylaromatic sulfonate sample to which the CaCl₂ was added, to        give results as mg Ca/g sulfonate.

Blended Alkylaromatic Sulfonates

Processes according to some embodiments further include optionalblending so as to obtain a blended alkylaromatic sulfonate composition.For instance, a linear alkyl benzene (LAB) composition may be blendedwith a precursor alkyl aromatic composition, followed by sulfonation andneutralization of the blend, and/or a linear alkyl benzene sulfonate(LAS) composition blended with an alkylaromatic sulfonate composition toform the blended alkylaromatic sulfonate composition.

That is, processes according to some embodiments further compriseblending a LAB composition with a precursor alkylaromatic composition(in accordance with any of the previously described alkylaromaticcompositions of various embodiments) to form a blended alkylaromaticprecursor. The blended alkylaromatic precursor is then sulfonated andneutralized in accordance with the previous descriptions of suchprocesses, to obtain the blended alkylaromatic sulfonate composition. Inparticular of these embodiments, blending the precursor alkylaromaticcomposition with a LAB composition advantageously prevents phaseseparation during sulfonation, such that it is not necessary to remove alight oil phase during sulfonation (as noted above with respect to someembodiments in accordance with FIG. 4). Thus, the resulting blendedalkylaromatic sulfonate composition may comprise a fraction of compoundsother than sulfonatable aromatics (e.g., 0.1 wt %-50 wt %, preferably0.1 wt %-30 wt %).

In some embodiments, the pre-sulfonation blend comprises 1 wt %-99 wt %LAB composition and 1 wt %-99 wt % precursor alkylaromatic composition.Preferred blend compositions of some embodiments include precursoralkylaromatic composition within a range from a low of any one of 10,20, 30, 40 or 50 wt %, to a high of 40, 50, 60, 70, or 80 wt %, providedthat the high end of the range is greater than the low end. Forinstance, preferred ranges include, for example, 10-30 wt %, 20-60 wt %,30-50 wt %, 30-60 wt %, and 40-70 wt % precursor alkylaromaticcomposition, the wt % based on the total mass of the blendedalkylaromatic precursor. The balance of the blended precursorcomposition comprises the LAB composition. The precursor alkylaromaticcomposition may be constituted as per any of the previously describedalkylaromatic compositions (e.g., as noted previously, comprisingsulfonatable aromatics, and particularly 1R, 1.5R, and/or 2+Ralkylaromatic compounds, within the range from a low of 35, 40, 45, 50,55, or 60 wt % to a high of 62, 65, 75, or 80 wt %, such wt % s based onthe mass of precursor alkylaromatic composition in the blend).

Advantageously, any conventional LAB composition, such as commerciallyavailable A225, may be used. LAB compositions according to someembodiments comprise at least 85 wt %, preferably at least 90 wt %, ofvarious isomers of alkylbenzenes having unbranched alkyl chain lengthfrom 8 to 20, preferably from 10 to 16, carbon atoms, with the phenylmoiety located on the 2-10, preferably the 2-5, carbon of the alkylchain. Thus, LAB compositions comprise at least 85 wt %, preferably atleast 90 wt %, more preferably at least 95 wt % (such as at least 98 wt%), of isomers of compounds in accordance with Formula (X) below:

where 6<x+y<18 (preferably where 8<x+y<14), and x and y are each atleast 1.

Conveniently, LAB compositions may be obtained from conventionalprocesses for alkylating, benzene to form LABs, which is well known inthe art.

Similarly, processes according to some embodiments also or instead mayfurther comprise blending a LAS composition with an alkylaromaticsulfonate composition (or blending a neutralized LAS composition with aneutralized alkylaromatic sulfonate composition) so as to obtain theblended alkylaromatic sulfonate composition.

Suitable LAS compositions may also vary widely in composition.Preferably, suitable LAS compositions are the corresponding sulfonatesof such LAB compositions. That is, suitable LAS compositions comprise atleast 85 wt %, preferably at least 90 wt %, more preferably at least 95wt % (such as at least 98 wt %) of isomers of compounds in accordancewith Formula (XI) below:

where x and y are as discussed above with respect to formula (X). Itwill be understood that, as with other sulfonate compounds describedherein, the LAS compounds in accordance with Formula (XI) are anionic,and therefore may exist in their anionic form or in a salt form (e.g.,with ionic bonding to a cationic species, such as Na⁺, K⁺, or the like).Therefore, a LAS compound may be characterized as a compound comprisingisomers in accordance with Formula (XI), and/or salts thereof.

Processes according to yet further embodiments may include both forms ofblending just described, i.e., such processes may include (i) blendingLAB compositions with a precursor alkylaromatic composition, (ii)sulfonating the blend, then (iii) further blending with a LAScomposition to form the blended alkylaromatic sulfonate composition.

Blended alkylaromatic sulfonate compositions according to variousembodiments may comprise 1-99 wt % of a LAS composition and 1-99 wt % ofthe alkylaromatic sulfonate composition comprising 1R, 1.5R, and/or 2+Ralkylaromatic sulfonates, which may be in accordance with any of theforegoing embodiments described with respect to such alkylaromaticsulfonates. Preferred amounts of alkylaromatic sulfonate composition inthe blended alkylaromatic sulfonate compositions include a range from alow of any one of 10, 20, 30, or 40 wt %, to a high of 30, 40, 50, 60,or 70 wt %, provided that the high end of the range is greater than thelow end. Particular examples include 20-60 wt %, such as 30-50 wt % or30-60 wt %, alkylaromatic sulfonate composition in the blendedalkylaromatic sulfonate compositions.

Blended alkylaromatic sulfonate compositions of some embodiments mayexhibit any one or more of the following properties:

-   -   Surfactant activity within the range from 25 to 95%, preferably        30 to 80%, 30 to 70%, or 40 to 60%, with ranges from any of the        foregoing low ends to any of the foregoing high ends also        contemplated in some embodiments.    -   Critical micelle concentration (CMC) within the range from        0.01-0.1 wt %, such as 0.01-0.05 wt %.    -   Draves wetting within the range from 5 to 25, preferably 5 to        20, more preferably 5 to 15 sec as determined at 21° C. for 0.1        wt % solution of the blended alkylaromatic sulfonate in water.    -   Ross-Miles Foam height within the range from 5 to 40 mm,        preferably 10 to 35 mm (initial); and/or 5 to 40 mm, preferably        10 to 35 mm (after 5 min), as determined at 21° C. for 0.1 wt %        solution of the blended alkylaromatic sulfonate in water.    -   Interfacial tension (IFT) of a 0.10 wt % solution in distilled        water within the range from 1.5 to 3.0, preferably 1.5 to 2.5        mN/m in mineral oil and distilled water interface.    -   Calcium tolerance within the range from 10 to 30 mg Ca/g blended        alkylaromatic sulfonate, such as from 15 to 25 mg Ca/g.

Omitting Hydrocarbon Mixture Treatment

In some embodiments, the previously-described hydrocarbon treatments maybe omitted. In this instance, the untreated hydrocarbon mixture may beused in the above-described methods in place of the precursoralkylaromatic composition—that is, the untreated hydrocarbon mixture ofsuch embodiments may be blended with LAB and sulfonated as describedabove with respect to blending the precursor alkylaromatic composition,or it may be sulfonated without blending, using sulfonation techniquesin accordance with the above-described sulfonation techniques.

Such embodiments may be particularly useful in combination withembodiments including one or more blending steps. That is, where anuntreated hydrocarbon mixture is to be utilized, such mixture ispreferably blended with a LAB composition (in accordance with any of theabove-described LAB compositions) and sulfonated. The sulfonatedcomposition is optionally further blended with a LAS compositionaccording to any of the above-described LAS compositions. Alternatively,the untreated hydrocarbon mixture of other embodiments is sulfonatedwithout blending, and the sulfonated product blended with a LAScomposition. The cost savings of omitting treatment may be quiteadvantageous, and the detriment to surfactant performance from thepresence of compounds other than sulfonatable aromatics may beadvantageously minimized through any of the just-described blending. Inembodiments in which a hydrocarbon mixture comprises substantially only1R alkylaromatics, 1.5R alkylaromatics, or 2+R alkylaromatics (inaccordance with embodiments previously described), blending one or moresuch hydrocarbon mixtures with a LAB composition (or sulfonating andblending with a LAS composition) is particularly advantageous, sincetreating such hydrocarbon mixtures may not be necessary to maintainacceptable or even superior surfactant performance.

Furthermore, in such embodiments, the hydrocarbon mixture may beobtained from any source—it need not be a refinery cut, and could indeedbe obtained as pure hydrocarbon of a desired composition (e.g.,purchased or formed through any means of synthesis such as alkylation ofa base benzene, naphthalene, or the like). The ordinarily skilledartisan will readily recognize any of the numerous ways in which a givenhydrocarbon mixture (e.g., one comprising alkylated naphthalenes and/ordi-alkyl benzenes, among others) may be obtained.

For instance, in some particular embodiments, a hydrocarbon mixturecomprising at least 80, preferably at least 90, more preferably at least95 wt % of di-alkylaromatic benzenes in accordance with any one ofFormulas (III), (IV), or (V) is blended with a LAB composition andsulfonated to obtain a blended alkylaromatic sulfonate composition.Alternatively, such hydrocarbon mixture comprising the di-alkylaromaticbenzene can be subjected to sulfonation, and the sulfonated productblended with a LAS composition to obtain the blended alkylaromaticsulfonate composition. Preferably, the pre-sulfonated blend (i.e., theblended alkylaromatic precursor comprising such hydrocarbon mixture andthe LAB composition) comprises from 2 to 60 wt %, preferably 2 to 40 wt%, more preferably from 2 to 25 or even 2 to 20 wt %, of thedi-alkylaromatic benzenes; and from 40 to 90 wt %, preferably 60 to 98wt %, more preferably from 75 to 98 wt % or even 80 to 98 wt % of theLAB composition. Likewise, the corresponding alkylaromatic sulfonatecomposition may comprise from 2 to 60 wt %, preferably 2 to 40 wt %,more preferably from 2 to 25 wt %, or even 2 to 20 wt %, of thedi-alkylaromatic sulfonates; and from 40 to 98 wt %, preferably 60 to 98wt %, more preferably from 75 to 98 wt %, or even 80 to 98 wt %, of thesulfonated LAB composition (e.g., a LAS composition corresponding to theLAB composition).

As another example, in yet other embodiments, a hydrocarbon mixturecomprising at least 80, preferably at least 90, more preferably at least95 wt % of one or more alkylated naphthalenes is blended with a LABcomposition and sulfonated, or sulfonated and then blended with a LAScomposition, to form a blended alkylaromatic sulfonate composition.Preferably, the alkylated naphthalenes are mono, di, and/ortri-alkylated. In some embodiments, each naphthalene is in accordancewith Formula (VII) (i.e., the hydrocarbon mixture of such embodimentscomprises isomers of alkylated naphthalenes each having structure inaccordance with Formula (VII)). In such embodiments, the pre-sulfonationblend (i.e., the blended alkylaromatic precursor formed by blending suchhydrocarbon mixtures with LAB compositions) comprises from 2 to 60 wt %,preferably 2 to 40 wt %, more preferably from 2 to 25 wt %, or even 2 to20 wt %, of the alkylated naphthalenes; and from 40 to 98 wt %,preferably 60 to 98 wt %, more preferably from 75 to 98 wt %, or even 80to 98 wt % of the LAB composition. Likewise, the blended alkylaromaticsulfonate composition preferably comprises from 2 to 60 wt %, preferably2 to 40 wt %, more preferably from 2 to 25 wt %, or even 2 to 20 wt %,of the corresponding sulfonated alkyl-naphthalenes; and from 40 to 98 wt%, preferably 60 to 98 wt %, more preferably from 75 to 98 wt %, or even80 to 98 wt %, of the sulfonated LAB composition (e.g., a LAScomposition corresponding to the LAB composition).

In yet further embodiments, the hydrocarbon mixture may comprisedi-alkyl benzenes (preferably having structures according to any one ormore of Formulas (III)-(V)) and alkylated naphthalenes (preferablymono-, di-, or tri-alkylated naphthalenes, more preferably havingstructure according to formula (VII)). The hydrocarbon mixture isblended with a LAB composition and sulfonated, and/or sulfonated andblended with a LAS composition, to form the blended alkylaromaticsulfonate. The pre-sulfonated blend comprises 2 to 40 wt %, preferably 2to 25 wt %, or even 2 to 20 wt %, of each of the di-alkyl benzenes andthe alkylated naphthalenes, with the balance formed by the LABcomposition. The post-sulfonated blend (i.e., the blended alkylaromaticsulfonate) likewise preferably comprises 2 to 40 wt %, more preferably 2to 25 or 2 to 20 wt %, of each of the corresponding di-alkyl benzenesulfonates and the corresponding alkyl naphthalene sulfonates, with thebalance formed by the LAS composition.

Such hydrocarbon mixtures (e.g., comprising di-alkyl benzenes and/oralkylated naphthalenes) may be obtained by any means, with no treatmentnecessary. For instance, alkylation or other synthetic processes may beused to form such compositions.

The blended alkylaromatic sulfonate compositions formed according tosuch embodiments may advantageously exhibit very low CMC, such as CMCwithin the range from 0.001 to 0.01 wt %. Alternatively, such blendedalkylaromatic sulfonate compositions may exhibit CMC that is at most1/10 of the CMC of the LAS composition (i.e., the sulfonated LABcomposition) in the absence of the sulfonated hydrocarbon mixture.

Such blended alkylaromatic sulfonate compositions may additionally haveIFT, Ca tolerance, and Draves Wetting that are each no more than 10%different from the IFT, Ca tolerance, and Draves Wetting of the LAScomposition in the absence of the sulfonated hydrocarbon mixture. Forinstance, where N is the Ca tolerance of the LAS composition, theblended alkylaromatic sulfonate may have Ca tolerance of at least 0.9Nand at most 1.1N (and likewise for IFT and Draves Wetting).

EXAMPLES Example 1: Effects of Extractions

A distillate feed was hydrotreated to reduce level of heteroatoms to 52ppm Sulfur and 1 ppm Nitrogen, then cut to a boiling range of 260°C.-340° C. and extract with NMP (66% treat rate, 0.5 wt % H₂O insolvent, 25° C.) to remove 77 wt % of 2-ring (and greater) aromatics inthe feed. The extracted hydrocarbon was recovered as Sample 1-1, and aportion of Sample 1-1 was retained for composition analysis, reported inTable X below.

The remaining portion of Sample 1 was extracted at a more severecondition with NMP (225% treat rate, 0.5 wt % H₂O in solvent, 25° C.) toconcentrate 1 ring aromatics the extract and generate Sample 1-2. Sample1-2 was extracted again with NMP (175% treat rate, 0.5 wt % H₂O insolvent, 25° C.) to further concentrate the aromatics in the extract andgenerate Sample 1-3.

An additional sample (Sample 1-4) was obtained as follows: Anotherportion of the distillate feed was hydrotreated to reduce the level ofheteroatoms to 52 ppm Sulfur and 1 ppm Nitrogen, cut to a boiling rangeof 260° C.-380° C. (a higher maximum boiling range as compared toSamples 1-3). This sample was then subjected to similar extractions aswith Sample 1-3: specifically, it was extracted with NMP (66% treatrate, 0.5 wt % H₂O in solvent, 25° C.) to remove 77% of 2-ring aromaticsin the feed, then extracted with NMP at a more severe condition (225%treat rate, 0.5 wt % H₂O in solvent, 25° C.) to concentrate the 1 ringaromatics in the extract, and then extracted again with NMP (175% treatrate, 0.5 wt % H₂O in solvent, 25° C.) to further concentrate thearomatic in the extract and generate Sample 1-4.

A further sample (Sample 1-5) was obtained as follows: Another portionof the distillate feed was hydrotreated to reduce the level ofheteroatoms to 52 ppm Sulfur and 1 ppm Nitrogen, cut to a boiling rangeof 170° C.-260° C. (lower than previous samples), and then subjected tothe same three NMP extractions as was Sample 1-4, in the same order.

A final sample (Sample 1-6) was obtained as follows: Another portion ofthe distillate feed was hydrotreated to reduce the level of heteroatomsto 52 ppm Sulfur and 1 ppm Nitrogen, cut to a boiling range of 170°C.-380° C. (broader than the previous samples), and then subjected tothe same 3 extractions, in the same order, as Samples 1-4 and 1-5 weresubjected to.

The distribution of saturates, 1R, 1.5R, and 2+R alkylaromatic compoundsin all 6 of these samples before sulfonation, measured by 2D-GC, isshown in Table 1.

TABLE 1 Compositions of hydrocarbon streams following extractions No. ofSample Severe SATS, 1R, 1.5R, 2 + R, Generated Carbon # EXT wt % wt % wt% wt % 1-1 C16-C21 0 78 12 8 2 1-2 C16-C21 1 46 23 23 8 1-3 C16-C21 2 3823 26 13 1-4 C16-C26 2 29 21 27 23 1-5 C10-C17 2 44 23 25 8 1-6 C10-C262 38 22 25 16

Samples 1-1 through 1-3 were further sulfonated and the resultingalkylaromatic sulfonate compositions were tested for Ca tolerance,wetting, foaming, IFT, and CMC. Results are reported in Table 2, alongwith a comparator LAS composition (A225, available from Huntsman)

TABLE 2 Surfactant properties of Example 1 sulfonates Ross-Miles IFT,mN/m, Draves Cotton Foam @ 21° C., mineral oil/de- Wetting @ mm, 0.1 wt% ionized water ml 1.0% CaCl₂ 21°, sec, 0.1 Initial, 5 min, 0.1% 0.5% toHaze No 50 CMC, % wt %, seconds mm mm surfactant surfactant Desired HighLow Low Low Low Low Low LAS 0.31 0.01-0.05 5.2 124 119 1.60 3.06 1-10.98  0.1-0.5 >500 71 52 9.44 5.96 1-2 1.05  0.5-1.0 203 15 13 6.63 4.011-3 0.91  0.5-1.0 >500 36 23 8.34 5.46

Due to their low foaming and good hardness tolerance, Samples 1-1through 1-3 are suitable for use as hydrotropes in liquid laundrydetergent formulation, e.g., added as 7-15 wt %, such as 11-12 wt % oreven 10 wt %, in the total detergent weight mixture or as emulsionbreaker (de-emulsifier). Additionally, the low foaming can make thesesamples good additives in several house hold and industry detergent todecrease foaming when it is not desired. Furthermore, the superior Catolerance demonstrated by the ml of CaCl₂ required to reach Haze No. 50for Samples 1-1 through 1-3 indicates the potential for thesecompositions to be advantageously employed in enhanced oil recoveryoperations.

Example 2: Sulfonation of Variously Extracted Precursor AlkylaromaticCompositions

Three sample precursor alkylaromatic compositions (2-1, 2-2, and 2-3)were obtained through a different number of severe extractions as shownbelow in Table 3, and analyzed for wt % of sulfonatable aromatics by2D-GC. The results (and number of severe extractions) are shown below,as compared to a commercial LAB 11 composition (Sample 2-C, which wasA225, a 2-dodecylbenzene with 98 wt % purity available from Huntsman)The first severe extraction (# Severe Extractions referenced in TableX+2˜, applicable to Samples 2-1 and 2-2) was with NMP (225% treat rate,0.5 wt % H₂O in solvent, 25° C.); the second severe extraction(applicable to Sample 2-1) was also with NMP (175% treat rate, 0.5 wt %H₂O in solvent, 25° C.).

TABLE 3 Pre-sulfonation material characterization # Severe SulfonatableSamples Extractions compound wt % Carbon # 2-C NA 98 C14-C22 2-1 2 69C16-C21 2-2 1 57 C16-C21 2-3 0 29 C16-C21

The A225 was sulfonated in accordance with the following procedure:

-   1. Added the alkylate to the glass reactor and started stirring.-   2. The stirred alkylate was cooled in ice-water to 10° C.-25° C.    during the drop wise addition of fuming sulfuric acid.-   3. Heated to 50° C. after finishing addition of the fuming sulfuric    acid.-   4. Held at 50° C. for 3.5 hours.

The sulfonation mixture was then subjected to the followingneutralization:

-   5. The sulfonation mixture was transferred to a dropping funnel and    added dropwise to a stirred and ice-cooled solution of diluted NaOH    such that the temperature of the mixture does not exceed 40° C. The    total weight of water and NaOH was 2010 g which is equivalent to    12.2% NaOH.-   6. The precipitated white slurry is transferred into two 1-liter    separatory funnels and the lower aqueous phase withdrawn    periodically.-   7. A total of 1046 g of lower aqueous slurry (sulfonated Sample 2-C)    was retained.

The resulting slurry was then purified as follows:

-   8. The slurry was poured into a 4-liter beaker with 460 g of    deionized water added.-   9. The slurry was stirred for 15 minutes and vacuum-filtered through    a 2.5 micron filter paper. The resulting gelatinous paste was    transferred into two heavyweight steel pans for drying in a 75° C.    oven to constant weight which required 3.5 days at this temperature.-   10. This yielded 331.9 g of sulfonated Sample 2-C.

Samples 2-1, 2-2, and 2-3 were each independently sulfonated accordingto the following procedure:

-   1. Added the sample to the glass reactor and started stirring.-   2. The stirred alkylate was cooled in ice-water to 10° C.-25° C.    during dropwise addition of fuming sulfuric acid.-   3. The mixture was heated to 50°-53° C. for 3.5 hours.-   4. The dark reaction mixture was cooled to room temp and poured into    a separatory funnel.-   5. The upper phase was separated to yield unsulfonatable oil    (reported for each sample in Table 4a below).

Samples 2-1, 2-2, and 2-3 were then each independently neutralized bydropwise addition of aqueous NaOH that was diluted with water to 300 gto yield an aqueous liquid containing a crystalline mass, for eachsample.

Each sample was then purified as follows:

-   6. Each crystalline mass-containing aqueous liquid was filtered to    yield a wet solid and a filtrate. Titration of the filtrate for    active was carried out to determine the activity of the sample.-   7. This aqueous solution, was poured into iron pans and concentrated    to dryness in a 75° C. oven.-   8. The resulting solids were extracted with hot IPA and suction    filtered.-   9. The IPA filtrate was concentrated on a rotary evaporated vacuum    to dryness. This yielded the amount of sulfonated product reported    in Table 4a below for each Sample.

Table 4a shows the charging materials, sulfonated product, and activityfor Samples 2-C, 2-1, 2-2, and 2-3. Table 4b below shows the conversionof total aromatics, and the conversion of each of the 1R, 1.5R, and 2+Raromatics (i.e., wt % of each type of aromatic sulfonated during thesulfonation reaction, as determined from 2D-GC).

TABLE 4a Sulfonation parameters and products for Example 2 Oil PhaseH₂SO₄ (g) Arom. Sulfo- Arom. + withdrawn Rings in nated Ac- Sam- massRings SO₃ during sulfonate product tivity ple (g) (mmol) (g) sulfonation(mmol) (g) (%) 2-C 246 1000 332.7 NA NA 331.9 90.3 2-1 124.1 313 100.060 183.5 14.6 68.4 2-2 137.4 247 96 79.2 180.4 22.8 76.2 2-3 247.3 16673.5 217.1 54.6 4.5 65.8

TABLE 4B Aromatic Conversions in Sulfonation of Example 2 Conversion ofConversion Conversion Conversion Sample Total Aromatics 1R 1.5R 2 + R2-1 80.50 wt % 64.26 wt % 86.98 wt % 96.28 wt % 2-2 79.72 wt % 67.42 wt% 88.92 wt % 92.79 wt % 2-3 56.07 wt % 34.11 wt % 67.05 wt % 100.00 wt% 

The mmol of aromatic rings in the sulfonate was calculated by combiningdata from 2D-GC, carbon weight percent, and C-NMR. First, the moles oftotal aromatic carbon per kg of sample was calculated from the wt % C ofthe sample and its fraction of aromatic carbon, as obtained by C-NMR:

${{{n\left( C_{AROMATIC} \right)}/{kg}}\mspace{14mu} {sample}} = {\frac{{wt}\mspace{14mu} \% \mspace{14mu} {C/100}*1000\mspace{14mu} g}{12\mspace{14mu} g\text{/}{mol}}*{\frac{\% \mspace{14mu} C\mspace{14mu} {Aromatic}}{100}.}}$

Next, the moles of aromatic rings per kg of sample were calculated bymultiplying the above-derived moles aromatic carbon by the 2D-GCobtained fraction of 1, 2, and 3-ring aromatics in the sample, dividedby the number of carbons per respective aromatic rings class andmultiplied by the number of rings in the respective class of aromatic asshown below (where “3RA” means 3-ring aromatic, “2RA” means 2-ringaromatics, and “1RA” means 1-ring aromatics):

Moles of aromatic rings/kg sample=(%3RA/100*n(C_(AROMATIC))/14*3+%2RA/100*n(C _(AROMATIC))/10*2+%1RA/100*n(C_(AROMATIC))/6).

CMC was determined at 22° C. in distilled water for each sulfonatedsample. FIGS. 5, 7, 9, and 11 each show a graph of surface tension(mN/m) vs. sulfonated Sample concentration in water (wt %), which wasused to determine CMC for each sulfonated Sample 2-C, 2-1, 2-2, and 2-3,respectively. Calcium tolerance was determined for each sulfonatedsample in distilled water (0.10 wt % solution) by titrating 50 g of a0.1% sample solution (0.05 g) with 1.00 wt % calcium chloride (3.64 mgCa/ml) to a haze value of 50. FIGS. 6, 8, 10, and 12 are each a graph ofml 1% CaCl₂ vs. Haze No.; the ml value of the 1% CaCl₂ solution at 50Haze was used to determine the calcium tolerance, based upon the valueof 3.64 mg Ca/ml to convert from ml of 1% CaCl₂ solution to g Carequired to bring the 0.05 g sample to Haze value 50.

Draves wetting was also determined for a 0.10 wt % solution of eachsulfonated sample in distilled water at 22° C.; Ross-Miles Foam heightwas determined at 22° C. for each sulfonated sample; and IFT was runagainst mineral oil at 22° C. in distilled water and recorded at 0.1 wt% and 0.5 wt % concentrations of each sulfonated sample in water.

The results of each test for each sulfonated sample are summarized inTable 5 below. As shown in Table 5, while the sulfonated productsobtained using only severe NMP extractions may have inferior cleaningdetergent properties as compared to the comparator commercial LAS, theyhave far superior calcium tolerance, indicating that they could beparticularly useful in enhanced oil recovery operations.

TABLE 5 Performance testing for Example 2 sulfonated samples Ross- IFT,Miles Ross-Miles IFT, 0.1% 0.5% Calcium Draves Foaming, Foaming, conc.,conc., Tolerance, Sample CMC, % Wetting(s) initial, mm 5 min, mm mN/mmN/m mCa/g 2-C 0.01-0.05 5.2 124 119 1.60 3.06 22.6 2-1 0.01-0.05 >50071 52 9.44 5.96 71.3 2-2  0.5-1.0 203 15 13 6.63 4.01 76.4 2-3 0.5-1.0 >500 36 23 8.34 5.46 66.2

Example 3: Blended Alkylaromatic Sulfonate Compositions

Portions of the un-sulfonated Samples 2-1, 2-2, and 2-3 were eachsulfonated to obtain sulfonated samples corresponding to each of Samples2-1, 2-2, and 2-3, and differing amounts of the unsulfonatable phaseresulting from the sulfonation reaction were removed from eachsulfonated sample. The sulfonated samples were then each blended with aseparately sulfonated A225 alkylate (2-dodecylbenzene with 98 wt %purity, from Huntsman), thereby obtaining blended alkylaromaticsulfonates. Table 6 below summarizes the blended alkylaromatic sulfonatesamples thusly created (including amounts of unsulfonatable oilremaining in each blend, and relative amounts of sulfonated product andsulfonated A225 alkylate used in each blend). In Table 6, the portion ofeach blend corresponding to the precursor alkylaromatic compositionsdescribed above in connection with various embodiments is the sum ofboth columns “Sulfonated product” and “unsulfonatable oil”(corresponding respectively to the sulfonates of the sulfonatablearomatics and compounds other than sulfonatable aromatics (e.g.,saturates) of the precursor alkylaromatic compositions).

TABLE 6 Example 3 Sample blends for performance testing A225 Derivedfrom Sulfonated Unsulfonatable alkylate Sample Ex. 2 Sample product (wt%) Oil (wt %) (wt %) 3-1 2-1 10 4 86 3-2 2-1 30 12 58 3-3 2-1 40 16 443-4 2-2 10 6 84 3-5 2-2 20 12 68 3-6 2-2 30 18 52 3-7 2-3 10 8 82 3-82-3 20 16 64 3-9 2-3 30 24 46

Draves Wetting testing was carried out on all the samples. In addition,Ross-Miles Foam, IFT, CMC, and Ca tolerance testing were carried out onSamples 3-2 and 3-5. The results are reported in Table 7 below, withtest results of the A225 LAS composition reported as Sample 3-C forcomparison. Draves wetting was determined at 21° C. for a 0.10 wt %solution of the sample in distilled water. Ross-Miles Foam height wasrun at 21° C. in distilled water for a 0.10 wt % solution in water, withdata recorded initially and after 5 minutes. Interfacial tension (IFT)was run against mineral oil at 21° C. in distilled water for 0.1 wt %sample in water, and Ca tolerance determined in the same manner asdescribed with respect to Example 2.

TABLE 7 Performance Testing of Example 3 Sample Blends Draves Ross-MilesIFT, mN/m, Wetting Foam @ 21° C., mineral @ 21° C. mm, 0.1 wt % oil/DIWCa Sam- 0.1 wt %, Initial, 5 mm, 0.1% CMC tolerance ple Second mm mmsurfactant Wt % Mg Ca/g 3-C 5.2 124 119 1.60 0.01-0.05 22.6 3-1 16 — — —3-2 11 34 30 2.49 0.01-0.1  23 3-3 17 — — — — — 3-4 8 — — — — — 3-5 8 1010 1.66 0.01-0.1  17 3-6 18 — — — — — 3-7 11 — — — — — 3-8 14 — — — — —3-9 18 — — — — —

The blending tests show some very interesting results. While thealkylaromatic sulfonate compositions according to Example 2 exhibitedfar superior Ca tolerance and Ross-Miles foaming to conventionalcommercial LAS, but inferior cleaning detergent properties such asDraves Wetting, IFT, and CMC, the blends of Example 3 indicate that theadvantageously low foaming may be maintained by blending alkylaromaticsulfonates with conventional LAS compositions. At the same time,however, significant gains are made in the detergent properties (Draveswetting, IFT, CMC) in the blends of Example 3, as compared to theproperties of alkylaromatic sulfonates of Example 2. However, the Catolerance advantage of the non-blended compositions of Example 2 is lostwhen blended with conventional LAS composition.

In sum, the data suggests that alkylaromatic sulfonate compositionsaccording to various embodiments provide substantial flexibility intheir employment; they may be blended to form detergent compositionswith excellent surfactant properties for detergent and similar cleaningapplications, which advantageously also exhibit very low foaming. Or,they may remain un-blended and be utilized in applications where high Catolerance is demanded, such as enhanced oil recovery, or ashydrotropes/emulsion breakers (de-emulsifiers).

Example 4: Blending Specific Compounds with LAS Compositions

A hydrocarbon mixture comprising high wt % of an alkylated naphthalenewas blended with LAS compositions to determine whether such blendpartners improve surfactant properties with LAS compositions. Inparticular, 2, 10, 20, and 40 wt % of sulfonated6,7-dimethyl-1-(4-methylpentyl)-Naphthalene was blended with A225(2-dodecylbenzene, 98 wt % purity, available from Huntsman) FIG. 13shows the CMC range measured for each blend. Surprisingly, blends as lowas 2 wt % and up to 20 wt % of the alkylated naphthalene in thesulfonated A225 composition yielded a significantly lower CMC value(0.001-0.01 wt %) as compared to the conventional LAS (sulfonated A225)composition on its own (CMC of 0.05-0.1 wt %). At the same time, theDraves Wetting and Ca tolerance of the conventional LAS were notsignificantly changed. In particular, regarding Ca tolerance, thevariation of all blends from the pure LAS lies within the experimentalerror. In some cases it even increases. The worst case data point is thedecrease of Ca-tolerance of 4%, which is still quite acceptable. Theworst case of wetting is observed in the 40 wt % case (40 wt % of thesulfonated 6,7-dimethyl-1-(4-methylpentyl)-naphthalene in the blend), inwhich case wetting is increased from 5 (pure LAS) to 9, which is stillconsidered good wetting for detergents.

The same trends are observed when blending di-alkylated benzenes withLAS. For instance, Table 8 shows Draves Wetting, CMC, Ca Tolerance,Ross-Miles Foam @ 21° C. (initial and 5-min, in mm) for blends ofp-dodecyl toluene (Sample 4-1) with A225; and blends of p-dioctylbenzene(Sample 4-2) with A225. Both Sample 4-1 and 4-2 are examples ofdi-alkylated benzenes according to some embodiments. Table 8 alsoincludes the performance data for6,7-dimethyl-1-(4-methylpentyl)-naphthalene (labeled as Sample 4-3),discussed above. The same performance test values for the commercialA225 LAS are reproduced from Table 7 to Table 8, for comparison.

TABLE 8 LAS Blend Study Performance Testing Ross-Miles Draves Wetting @Foam @ 21° C., Ca tolerance 21° C. mm, 0.1 wt % CMC Mg Ca/g Blend 0.1 wt%, Second Initial, mm 5 min, mm Wt % sulfonate Detergent <20 — — <0.1 ~22.6 Criteria 100% A225 5.2 124 119 0.01-0.05 22.6 100 wt % 4-1 2.1 135127 0.01-0.05 158.7 40/60 wt % 6.0 160 150 0.001-0.01  20.3 (4-1/A225)10/90 wt % 7.9 160 150 0.001-0.01  26.0 (4-1/A225) 100% 4-2 7.5 108 890.01-0.05 0 40/60 wt % 6.1 150 135 0.001-0.01  22.7 (4-2/A225) 10/90 wt% 6.4 160 148 0.001-0.01  23.7 (4-2/A225) 100% 4-3 >500 15 10 0.06-0.13131.04 40/60 wt % 9.0 130 110 0.01-0.1  21.6 (4-3/A225) 20/80 wt % (4-7.0 130 120 0.001-0.01  31.4 3/A225) 10/90 wt % 7.0 140 120 0.001-0.01 22.2 (4-3/A225) 2/98 wt % 6.0 130 120 0.001-0.01  29.4 (4-3/A225)

In all cases, independent of substitution position and length (withinthe bounds of total carbon numbers in the various embodiments describedherein), detergent criteria are met when up to 40 wt % of the blendpartner compositions are added to the conventional sulfonated A225.

This suggests that blending conventional LAS compositions withhydrocarbon mixtures comprising high wt % (e.g., at least 90, 95, 98,99, or even 100 wt %) of a particular compound or class of compounds(e.g., alkylated naphthalenes) may provide substantial advantages tosurfactant properties of the blended alkylaromatic sulfonate.

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For this reason, then, reference shouldbe made solely to the appended claims for purposes of determining thetrue scope of the present invention. The contents of all referencescited herein are incorporated by reference in their entirety.

1. A process comprising: (a) blending a hydrocarbon mixture comprisingone or both of alkylated naphthalenes and di-alkyl benzenes with alinear alkyl benzene (LAB) composition so as to obtain a blendedalkylaromatic precursor comprising (i) from 2 to 60 wt % of thealkylated naphthalenes, and/or (ii) from 2 to 60 wt % of the di-alkylbenzenes, provided that total wt % of alkylated naphthalenes anddi-alkyl benzenes in the blended alkylaromatic precursor does not exceed80 wt %; wherein the LAB composition comprises at least 95 wt % ofisomers of one or more compounds each in accordance with Formula (X):

where 6<x+y<18, and x and y are each at least 1; and further wherein thealkylated naphthalenes are selected from the group consisting ofmono-alkylated naphthalenes, di-alkylated naphthalenes, tri-alkylatednaphthalenes, and combinations thereof, and the di-alkylbenzenes areeach in accordance with any one of Formulas (III), (IV), or (V) below:

where, in each of Formulas (III)-(V), R¹ and R³ are each independentlyC₁-C₁₅ alkyl that is either unbranched or, if branched, has pendentchains no longer than 2 carbon atoms; and (b) sulfonating the blendedalkylaromatic precursor composition to obtain a blended alkylaromaticsulfonate composition.
 2. The process of claim 1, wherein the alkylatednaphthalenes each have structure in accordance with Formula (IX)

where each of R¹³, R¹⁴, R¹⁵, and R¹⁶ is independently selected from Hand C₁-C₁₅ alkyl, provided that the total number of carbon atoms inFormula (IX) does not exceed 30, and furthermore wherein each of R¹³-R¹⁵is either unbranched, or has branching such that pendent chains containno more than 2 carbon atoms.
 3. The process of claim 1, wherein thehydrocarbon mixture comprises at least 95 wt % of the alkylatednaphthalenes, and the blended alkylaromatic precursor comprises (i) from2 to 60 wt % of the alkylated naphthalenes, and (ii) from 40 to 98 wt %of the LAB composition.
 4. The process of claim 3, wherein the blendedalkylaromatic precursor comprises (i) from 2 to 25 wt % of the alkylatednaphthalenes, and (ii) from 75 to 98 wt % of the LAB composition.
 5. Theprocess of claim 2, wherein each of the alkylated naphthalenes is atri-alkyl-substituted naphthalene, such that one of R¹³-R¹⁵ is H.
 6. Theprocess of claim 4, wherein R¹³ is H, R¹⁴ is C₄-C₁₂ alkyl, and R¹⁵ andR¹⁶ are each C₁-C₃ alkyl.
 7. The process of claim 5, wherein each of thealkylated naphthalenes is 6,7-dimethyl-1-(4-methylpentyl)-Naphthalene.8. The process of claim 1, wherein the hydrocarbon mixture comprises atleast 95 wt % of the di-alkylbenzenes, and the blended alkylaromaticprecursor comprises (i) from 2 to 60 wt % of the di-alkylbenzenes, and(ii) from 40 to 98 wt % of the LAB composition.
 9. The process of claim8, wherein the blended alkylaromatic precursor comprises (i) from 2 to20 wt % of the di-alkylbenzenes, and (ii) from 80 to 98 wt % of the LABcomposition.
 10. The process of claim 1, wherein the blendedalkylaromatic sulfonate composition exhibits Critical micelleconcentration (CMC) that is at most 1/10 of the CMC of the sulfonatedLAB composition in the absence of the sulfonated hydrocarbon mixture.11. A process comprising: (a) sulfonating a hydrocarbon mixturecomprising one or both of alkylated naphthalenes and di-alkyl benzenes,thereby obtaining a sulfonated hydrocarbon mixture comprising one orboth of sulfonated alkyl naphthalenes and sulfonated di-alkyl benzenes;(b) forming a blended alkylaromatic sulfonate composition by blendingthe sulfonated hydrocarbon mixture with a linear alkylbenzene sulfonate(LAS) composition comprising at least 95 wt % of isomers of one or morecompounds each in accordance with Formula (XI), or a salt thereof:

where 6<x+y<18, and x and y are each at least 1; wherein the blendedalkylaromatic sulfonate composition comprises (i) from 2 to 60 wt % ofthe sulfonated alkyl naphthalenes, and/or (ii) from 2 to 60 wt % of thesulfonated di-alkylbenzenes, provided that the total wt % of sulfonatedalkyl naphthalenes and sulfonated di-alkylbenzenes in the blendedalkylaromatic sulfonate composition does not exceed 80 wt %; and furtherwherein the alkylated naphthalenes are selected from the groupconsisting of mono-alkylated naphthalenes, di-alkylated naphthalenes,tri-alkylated naphthalenes, and combinations thereof, and thedi-alkylbenzenes are each in accordance with any one of Formulas (III),(IV), or (V) below:

where, in each of Formulas (III)-(V), R¹ and R³ are each independentlyC₁-C₁₅ alkyl that is either unbranched or, if branched, has pendentchains no longer than 2 carbon atoms.
 12. The process of claim 11,wherein the alkylated naphthalenes each have structure in accordancewith Formula (IX):

where each of R¹³, R¹⁴, R¹⁵, and R¹⁶ is independently selected from Hand C₁-C₁₅ alkyl, provided that the total number of carbon atoms inFormula (IX) does not exceed 30, and furthermore wherein each of R¹³-R¹⁵is either unbranched, or has branching such that pendent chains containno more than 2 carbon atoms.
 13. The process of claim 11, wherein thehydrocarbon mixture comprises at least 95 wt % of the alkylatednaphthalenes, and the blended alkylaromatic sulfonate compositioncomprises (i) from 2 to 60 wt % of the sulfonated alkyl naphthalenes,and (ii) from 40 to 98 wt % of the LAS composition.
 14. The process ofclaim 11, wherein the hydrocarbon mixture comprises at least 95 wt % ofthe di-alkylbenzenes, and the blended alkylaromatic sulfonatecomposition comprises (i) from 2 to 60 wt % of the sulfonated di-alkylbenzenes, and (ii) from 40 to 98 wt % of the LAS composition.
 15. Theprocess of claim 11, wherein the blended alkylaromatic sulfonatecomposition exhibits CMC that is at most 1/10 of the CMC of the LAScomposition in the absence of the sulfonated hydrocarbon mixture. 16.The process of claim 1, wherein the blended alkylaromatic sulfonatecomposition has CMC within the range from 0.001 to 0.01 wt %.
 17. Theprocess of claim 10, wherein the blended alkylaromatic sulfonatecomposition has Interfacial Tension (IFT), Ca tolerance, and DravesWetting that are each no more than 10% different from the IFT, Catolerance, and Draves Wetting, respectively, of the sulfonated LABcomposition in the absence of the sulfonated hydrocarbon mixture.
 18. Acomposition comprising: (a) 2 to 60 wt % of sulfonated alkylnaphthalenes that are the sulfonation reaction product ofalkylnaphthalenes each having structure in accordance with Formula (IX):

(b) where each of R¹³, R¹⁴, R¹⁵, and R¹⁶ is independently selected fromH and C₁-C₁₅ alkyl, provided that the total number of carbon atoms inFormula (IX) does not exceed 30, and furthermore wherein each of R¹³-R¹⁵is either unbranched, or has branching such that pendent chains containno more than 2 carbon atoms; and (c) 40 to 98 wt % of a linearalkylbenzene sulfonate (LAS) composition comprising at least 95 wt % ofisomers of one or more compounds each in accordance with Formula (XI):

where 6<x+y<18, and x and y are each at least
 1. 19. The composition ofclaim 18, wherein R¹¹ and R¹² are each C₁-C₃ alkyl, and R¹⁰ is C₄-C₁₂alkyl.
 20. The composition of claim 19, wherein each of the alkylatednaphthalenes is 6,7-dimethyl-1-(4-methylpentyl)-Naphthalene.
 21. Thecomposition of claim 18, having CMC within the range from 0.001 to 0.01wt %.
 22. The composition of claim 21, having Interfacial Tension (IFT),Ca tolerance, and Draves Wetting that are each no more than 10%different from the IFT, Ca tolerance, and Draves Wetting, respectively,of the LAS composition in the absence of the sulfonated hydrocarbonmixture.